US4241197A - Graft copolymers containing (meth)acrylic acid or (meth)acrylic acid esters - Google Patents

Graft copolymers containing (meth)acrylic acid or (meth)acrylic acid esters Download PDF

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Publication number
US4241197A
US4241197A US06/019,363 US1936379A US4241197A US 4241197 A US4241197 A US 4241197A US 1936379 A US1936379 A US 1936379A US 4241197 A US4241197 A US 4241197A
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weight
meth
acrylic acid
graft
copolymer
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US06/019,363
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Ulrich Steffen
Heinrich Alberts
Richard Prinz
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers

Definitions

  • This invention relates to graft copolymers of ethylene copolymers as the graft base and a mixture of acrylonitrile, aromatic monovinyl compounds and (meth)acrylic acid or (meth)acrylic acid esters as the graft monomers and to a process for the production thereof.
  • the present invention relates to graft copolymers of ethylene copolymers and olefinically unsaturated monomers, characterised in that they contain graft-polymerised units of mixtures of (meth)acrylonitrile, one or more aromatic monovinyl compounds, (meth)acrylic acid or (meth)acrylic acid ester on ethylene/vinyl ester copolymers.
  • Ethylene/vinyl ester copolymers containing from 1 to 75% by weight, preferably from 35 to 50% by weight, of copolymerised vinyl esters may be used as graft bases.
  • Esters of monocarboxylic acids containing from 1 to 10 carbon atoms in the alkyl radical are used as the vinyl esters, vinyl acetate being preferred.
  • the ethylene/vinyl ester copolymers may have Mooney viscosities ML 4/100° C., as measured in accordance with DIN 53 523, of from 15 to 80, preferably from 20 to 45, and intrinsic viscosities [ ⁇ ] of from 0.5 to 1.5 dl/g. These copolymers are soluble in hydrocarbons and, where they have relatively high vinyl ester contents, also in alcohols.
  • the monomers to be grafted may be selected from (meth)acrylonitrile, aromatic monovinyl compounds such as styrene, ⁇ -methyl styrene and nucleus-substituted styrenes, such as halogenated and C 1 -C 4 alkylated styrenes, (meth)acrylic acid and (meth)acrylic acid C 1 -C 12 alkyl esters.
  • acrylonitrile styrene and (meth)acrylic acid C 1 -C 4 alkyl esters are preferred.
  • the mixture of substances used consists of:
  • (III) from 0.1 to 15%, by weight, preferably from 0.5 to 12% by weight, or (meth)acrylic acid or a (meth)acrylic acid alkyl ester.
  • the graft copolymers obtained consist of:
  • (B) from 90 to 20%, by weight, preferably from 85 to 75%, by weight, of grafted resin phase obtained by copolymerising (meth)acrylonitrile, one or more aromatic monovinyl compounds and (meth)acrylic acid or a (meth)acrylic acid alkyl ester.
  • the resin phase consists of:
  • (III) from 0.1 to 15%, by weight, preferably from 0.5 to 12%, by weight, of (meth)acrylic acid or a (meth)acrylic acid alkyl ester.
  • graft copolymers have intrinsic viscosities of from 0.4 to 2.0, preferably from 0.6 to 1.5 dl/g, as measured in dimethyl formamide at 25° C.
  • the monomers are largely grafted onto the graft base.
  • small quantities of ungrafted copolymer and ungrafted base may be present.
  • the grafting reaction may be carried out in homogeneous or heterogeneous phase.
  • the type of solvent used will be determined by the vinyl ester content of the copolymer.
  • the preferred solvents are aromatic hydrocarbons, such as benzene, toluene and chlorobenzene.
  • alcohols preferably t-butanol, are used as solvents.
  • the grafting reaction onto ethylene/vinyl ester copolymers may also be carried out in bulk. Bulk grafting is best carried out continuously.
  • the average residence time in the reactor and the reaction temperature have to be adapted to the decomposition constant and concentration of the initiator in order to obtain a certain conversion and a sufficiently high molecular weight. This process guarantees a relatively uniform chemical distribution of the monomers in the resin phase.
  • the graft copolymerisation reaction may be initiated by irradiation or by radical-forming initiators.
  • Suitable polymerisation initiators include azo compounds, such as azo-bis-isobutyronitrile and, in particular, percompounds, such as isopropyl peroxy dicarbonate, ⁇ -ethyl hexyl peroxy dicarbonate, cyclohexyl peroxy dicarbonate, t-butyl perpivalate, t-butyl peroctoate, t-butyl perneodecanoate, diacetyl peroxide, lauroyl peroxide, succinyl peroxide and dibenzoyl peroxide.
  • the amount of initiator is from 0.1 to 1.0, by weight, preferably from 0.3 to 0.5%, by weight, based on the monomer mixture used.
  • the graft polymerisation reaction is carried out at temperatures of from 40° to 250° C., preferably from 60° to 120° C.
  • the graft polymerisation reaction is preferably started at relatively low temperatures, for example from 60° to 70° C., and completed at temperatures of from 80° to 100° C.
  • the grafting reaction may also be carried out in aqueous heterogeneous phase.
  • the graft polymerisation reaction is preferably initiated by heating a solution of ethylene/vinyl ester copolymer in a mixture of the above-mentioned monomers to a reaction temperature of from 60° to 90° C. in the presence of from 0.01 to 0.5%, by weight, of a peroxide of the above-mentioned type.
  • graft polymerisation is completed by bead polymerisation at from 80° to 100° C. by the addition of a mixture of water and a dispersant solution.
  • the ratio of the aqueous phase to the organic phase should amount to from 2:1 to 5:1.
  • Suitable dispersants are, for example, polyvinyl alcohol, partially hydrolysed polyvinyl acetate, cellulose derivatives, such as methyl or ⁇ -hydroxy ethyl cellulose, styrene/acrylic acid or hydrolysed styrene/maleic acid anhydride copolymers, methacrylic acid/methyl methacrylate copolymers, polyacrylamide or polyacrylic acid.
  • the dispersants are used in quantities of from 0.01 to 3% by weight, preferably from 0.5 to 2%, by weight, based on the organic phase used.
  • the graft base undergoes partial cross-linking. This leads to improved mechanical properties, for example higher impact strength, and better processibility.
  • the same effect may also be obtained by completing the polymerisation of a graft copolymer produced in bulk or in solution in a polymerisation screw at from 120° to 250° C. in the presence of a peroxide.
  • the methyl cyclohexane (MCH) phase contains ungrafted ethylene/vinyl acetate copolymer and a copolymer having few or short graft branches.
  • the ungrafted resin and the graft base of low molecular weight are fractionated in the dimethyl formamide (DMF) phase.
  • the analytical values are indicative of differently grafted base which is partly attributable to the wide molecular weight distribution of the base.
  • fractions of ungrafted base and free resin phase are with certainty very small because no further separation was possible by additional fractionation.
  • the products obtained in accordance with the present invention are suitable for use as coating materials and thermoplastically processible plastics. They may be processed without difficulty in the machines commonly used in thermoplast technology.
  • Extruded or injection-moulded articles have a high surface gloss which could not be obtained in the absence of acrylates as graft activators.
  • the elastomer phase and resin phase do not disintegrate under processing conditions.
  • Table 2 shows the test results of the graft copolymers prepared in accordance with Examples 1 to 12. The tests were carried out in accordance with the following Standards:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
US06/019,363 1978-03-16 1979-03-12 Graft copolymers containing (meth)acrylic acid or (meth)acrylic acid esters Expired - Lifetime US4241197A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782811549 DE2811549A1 (de) 1978-03-16 1978-03-16 (meth-)acrylsaeure oder (meth-)acrylsaeureester enthaltende pfropfcopolymerisate
DE2811549 1978-03-16

Publications (1)

Publication Number Publication Date
US4241197A true US4241197A (en) 1980-12-23

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US06/019,363 Expired - Lifetime US4241197A (en) 1978-03-16 1979-03-12 Graft copolymers containing (meth)acrylic acid or (meth)acrylic acid esters

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Country Link
US (1) US4241197A (enrdf_load_stackoverflow)
EP (1) EP0004308B1 (enrdf_load_stackoverflow)
JP (1) JPS54127496A (enrdf_load_stackoverflow)
DE (2) DE2811549A1 (enrdf_load_stackoverflow)
ES (1) ES478668A1 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5229456A (en) * 1988-03-29 1993-07-20 Rohm And Haas Company Graft copolymers and blends thereof with polyolefins
US5300570A (en) * 1989-03-01 1994-04-05 Rohm And Haas Company Plastic articles with compatibilized barrier resin
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3008747A1 (de) * 1980-03-07 1981-09-24 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von vernetzten pfropfcopolymerisaten

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742090A (en) * 1968-05-09 1973-06-26 Toray Industries Thermoplastic resin composition containing an ethylene-vinyl acetate graft copolymer
US3855353A (en) * 1972-03-30 1974-12-17 Bayer Ag Graft polymers based on ethylene copolymers
US4107109A (en) * 1977-03-22 1978-08-15 E. I. Du Pont De Nemours And Company Reactive compositions and polymers made therefrom

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900967C3 (de) * 1969-01-09 1974-10-31 Wacker-Chemie Gmbh, 8000 Muenchen Verwendung eines Redoxkatalysatorsystems zur Herstellung von gepfropften Äthylen-Vinylacetatcopolymer-Dispersionen
BE786297A (fr) * 1971-07-15 1973-01-15 Bayer Ag Composition de moulage thermoplastico-elastique
JPS5418315B2 (enrdf_load_stackoverflow) * 1972-05-17 1979-07-06
JPS5217593A (en) * 1975-07-31 1977-02-09 Sumitomo Chem Co Ltd Process for producing high-impact resins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742090A (en) * 1968-05-09 1973-06-26 Toray Industries Thermoplastic resin composition containing an ethylene-vinyl acetate graft copolymer
US3855353A (en) * 1972-03-30 1974-12-17 Bayer Ag Graft polymers based on ethylene copolymers
US4107109A (en) * 1977-03-22 1978-08-15 E. I. Du Pont De Nemours And Company Reactive compositions and polymers made therefrom

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5229456A (en) * 1988-03-29 1993-07-20 Rohm And Haas Company Graft copolymers and blends thereof with polyolefins
US5433984A (en) * 1988-03-29 1995-07-18 Rohm And Haas Company Plastic articles with compatibilized barrier resin
US5300570A (en) * 1989-03-01 1994-04-05 Rohm And Haas Company Plastic articles with compatibilized barrier resin
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods

Also Published As

Publication number Publication date
DE2961850D1 (en) 1982-03-04
ES478668A1 (es) 1979-06-01
JPS54127496A (en) 1979-10-03
EP0004308B1 (de) 1982-01-20
DE2811549A1 (de) 1979-09-20
EP0004308A2 (de) 1979-10-03
JPS6227088B2 (enrdf_load_stackoverflow) 1987-06-12
EP0004308A3 (en) 1979-10-17

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